Multifunctional biocomposite additive compositions and methods

ABSTRACT

Biocomposite compositions and compositions, which include dried distillers solubles, and which can be used in making biocomposite compositions are described. Methods for preparing the compositions are also described.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a CONTINUATION application of U.S. patentapplication Ser. No. 14/087,229, filed Nov. 22, 2013, which is acontinuation application of U.S. patent application Ser. No. 13/892,354,filed May 13, 2013, which is a Continuation of U.S. application Ser. No.12/466,336, (now U.S. Pat. No. 8,449,986), filed on May 14, 2009, whichclaims the benefit and priority of U.S. Provisional Application No.61/053,196, filed on May 14, 2008 and entitled, BIOELASTOMERS DERIVEDFROM CO-PRODUCTS OF BIOFUEL PRODUCTION. U.S. patent application Ser. No.12/466,336 is a continuation-in-part of U.S. application Ser. No.12/398,984, (now U.S. Pat. No. 7,937,850), filed on Mar. 5, 2009 andentitled, METHODS AND APPARATUS FOR DRYING CONDENSED DISTILLER'SSOLUBLES (CDS) TO PRODUCE DRIED DISTILLER'S SOLUBLES (DDS), which claimsthe benefit and priority of U.S. Provisional Application Ser. No.61/068,191, filed on Mar. 5, 2008 and entitled, APPARATUS AND METHODSFOR THE PRODUCTION OF DRIED CDS, the disclosures of each crossreferenced application are incorporated herein by reference in theirentireties.

FIELD OF THE INVENTION

The present invention relates to biocomposite compositions andcompositions that can be used in biocomposites. The present inventionalso includes methods of making the compositions.

BACKGROUND OF THE INVENTION

A variety of agents are used to form thermoplastic materials. Theseagents include compatibility agents, foaming agents as well as meltagents, which lower processing temperatures of plastics and othermaterials. Compatibility agents, melt agents and foaming agents canreduce the cost and consumption of thermoplastic or thermoactivematerials. Accordingly, there remains a need for an inexpensivebiologically derived material that can reduce the cost and consumptionof plastic or thermoactive materials. There is also a need forinexpensive and energy efficient methods of producing biocompositematerials.

Recycled mixed plastics from domestic and commercial waste are generallyincompatible in view of processing in a shaping process, such asextrusion. Mixtures of these plastics have led to materials that can beused in products having low physical and mechanical demands.Compatibility agents allow mixtures of incompatible plastics to bemolded into generally uniform materials. Compatibility agents that havebeen used are generally chemical agents, such as polystyrol andpolybutadiene. These and other chemical compatibility agents aregenerally toxic and expensive. Similarly, chemical melt agents aregenerally toxic and expensive. Hence, there is a need for compatibilityand melt agents that are inexpensive as well as non-toxic.

Foaming agents are frequently used in the production of variouspolymeric foamed materials. The foaming agents are generally physicalblowing agents such as nitrogen or carbon dioxide in a supercriticalstate and are injected into a molten polymer. The blowing agents producemicroscopic cells throughout a polymer, which results in a foamedpolymer. This process requires expensive equipment and materials. Thusthere is a need for a foaming agent that is inexpensive and simple touse.

SUMMARY OF THE INVENTION

Methods, apparatus and compositions disclosed herein may resolve many ofthe needs and shortcomings discussed above and will provide additionalimprovements and advantages that may be recognized by those of ordinaryskill in the art upon review of the present disclosure.

DDS biocomposite additive compositions are disclosed herein. In oneaspect, the DDS biocomposite additive compositions comprise about 30wt-% to about 90 wt-% dried distiller's solubles, about 5 wt-% to about20 wt-% metal oxide; and about 5 wt-% to about 50 wt-% fiber. In someembodiments, the compositions further comprise about 1 wt-% to about 15wt-% latex, acrylic latex or other latex compound.

Methods for producing a DDS biocomposite additive are also describedherein. In one aspect the method comprises combining a mixturecomprising about 30 to about 90 wt-% dried distiller's solubles, about 5to about 20 wt-% metal oxide and about 5 to about 50 wt-% fiber; anddrying the mixture in a pulsed drying gas stream using a pulsecombustion dryer.

Biopolymer compositions are also disclosed herein. In one aspect thebiopolymer comprises about 80 wt-% to about 99.5 wt-% of athermoplastic, thermoset, resin, polymer adhesive material, or mixturesthereof, about 0.15 wt-% to about 10 wt-% of dried distiller's solubles,about 0.025 wt-% to about 4.0 wt-% of a metal oxide; and about 0.025wt-% to about 10 wt-% fiber. In some embodiments, the biopolymercomposition also includes about 0.005 wt-% to about 5 wt-% of latex,acrylic latex, or other latex compound.

Methods of using the DDS biocomposite additive for making foamedcompositions are also disclosed herein. In addition, methods of usingthe DDS biocomposite additive for lowering the processing temperature ofa thermoplastic material and for processing incompatible thermoplasticmixtures into homogeneous thermoplastic compositions are also describedherein.

Other features and advantages of the compositions and methods disclosedherein will become apparent from the following detailed description andfrom the claims.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIGS. 1A and 1B illustrate by a flow chart specific embodiments of thepreparation of the dried distiller's solubles biocomposite additive.

FIG. 2A illustrates by schematic diagram an embodiment of the pulsecombustion dryer according to aspects of the present inventions.

FIG. 2B illustrates by schematic diagram a cross-section of anembodiment of the drying chamber according to aspects of the presentinventions.

All Figures are illustrated for ease of explanation of the basicteachings of the present inventions only; the extensions of the Figureswith respect to number, position, order, relationship and dimensionswill be explained or will be within the skill of the art after thefollowing description has been read and understood. Further, theapparatus, materials and other operational parameters to conform tospecific size, dimension, force, weight, strength, velocity,temperatures, flow and similar requirements will likewise be within theskill of the art after the following description has been read andunderstood.

Where used to describe the drawings, the terms “top,” “bottom,” “right,”“left,” “forward,” “rear,” “first,” “second,” “inside,” “outside,” andsimilar terms may be used, the terms should be understood to referencethe structure and methods described in the specification and illustratedin the drawings as they generally correspond to their with the apparatusand methods in accordance with the present inventions as will berecognized by those skilled in the art upon review of the presentdisclosure.

DETAILED DESCRIPTION OF THE INVENTION

A DDS biocomposite additive as a composition, including variouscomponents of the DDS biocomposite additive, as well as, methods for theproducing the DDS biocomposite additive are described herein. Inaddition, biopolymer compositions that contain the DDS biocompositeadditive, as well as methods of producing the biopolymer compositionsare also described. Properties of the DDS biocomposite additive for usein producing biopolymer compositions are also described, including itsuse as a foaming agent, an agent for reducing thermoplastic processingtemperatures and its use as a compatibilizing additive for incompatiblethermoplastic mixtures.

The Figures generally illustrate various exemplary embodiments of theDDS production apparatus 10, compositions, and methods. The particularexemplary embodiments illustrated in the Figures have been chosen forease of explanation and understanding. These illustrated embodiments arenot meant to limit the scope of coverage, but, instead, to assist inunderstanding the context of the language used in this specification andin the claims. Accordingly, variations of the DDS production apparatus10, compositions, and methods that differ from the illustratedembodiments may be encompassed by the appended claims.

DEFINITIONS

As used herein, condensed distiller's solubles (CDS) refers to thegenerally soluble portion of whole stillage (i.e. thin stillage)condensed by evaporation into a syrup.

As used herein, dried distiller's solubles (DDS) refers to the generallysoluble portion of whole stillage in dried form.

As used herein, “glass transition point” or “Tg” refers to thetemperature at which a particle of a material, such as a plastic orpolymer reaches a “softening point” so that it has a viscoelastic natureand can be more readily compacted. Below Tg a material is in its “glassstate” and has a form that cannot be as readily deformed under simplepressure. As used herein, “melting point” or “Tm” refers to thetemperature at which a material, such as a plastic or polymer melts andbegins to flow. Suitable methods for measuring these temperaturesinclude differential scanning calorimetry (DSC), dynamic mechanicalthermal analysis (DTMA) and thermal mechanical analysis (TMA).

As used herein, weight percent (wt-%) percent by weight, % by weight andthe like are synonyms that refer to the concentration of a substance asthe weight of that substance divided by the weight of the compositionand multiplied by 100. Unless otherwise specified, the quantity of aningredient refers to the quantity of active ingredient.

As used herein, the term “about” modifying any amount refers to thevariation in that amount encountered in real world conditions ofproducing materials, such as DDS additives, polymers or compositematerials, e.g., in the laboratory, pilot plant or production facility.For example, an amount of an ingredient employed in a mixture whenmodified by “about” includes the variation and degree of care typicallyemployed in measuring in a plant or laboratory producing a material orpolymer. For example, the amount of a component of a product whenmodified by “about” includes the variation between batches in a plant orlaboratory and the variation inherent in the analytical method. Whetheror not modified by “about”, the amounts include equivalents to thoseamounts. Any quantity stated herein and modified by “about” can also beemployed in the present invention as the amount not modified by about.

A DDS biocomposite additive may comprise a number of materials, with themajor material being DDS, or other material containing vegetableproteins. Other material containing vegetable proteins include, withoutlimitation, soy protein isolate, corn gluten meal, forms of distiller'sdried grains and residual amino acid/proteins from CDS processing. Anumber of methods are used to remove starch from the primary vegetableprotein material. The material may be processed to a fine powder formranging from particle size 30 mesh to well into the nanosize particlerange.

Stillage may be fractionated into various stillage fractions including asettleable fraction and a suspended fraction. The settleable fractionincludes non-dissolved settleable materials that generally settle out ofthe water component. In various aspects, the settleable fraction isknown in the industry as Distiller's Wet Grains (DWG) in the moist formand Dried Distiller's Grains (DDG) in the substantially dried form. Thesuspended fraction includes the generally non-settleable materials thatremain suspended, solubilized, and/or dissolved in the water componentof the stillage. The suspended fraction, for example, may includedissolved materials, colloidal materials, and/or non-colloidal materialsthat are sufficiently fine and/or of low specific gravity that theygenerally remain in suspension.

Upon removal of the settleable fraction from the stillage, theremainder, which includes the suspended fraction is termed thinstillage. The thin stillage, which may include a large fraction ofwater, may be concentrated in, for example, an evaporator, which removesa portion of the water from the thin stillage to produce syrup. As usedherein, the term Condensed Distiller's Solubles (CDS) encompasses thesuspended fraction of stillage, and includes thin stillage and syrupderived from thin stillage. CDS may be generally liquid, syrup or otherviscous fluid, or slurry, paste, or other non-Newtonian fluid, and theCDS may include various agglomerations, aggregations, non-homogeneities,and/or clumps of material. Dried Distiller's Solubles (DDS) as usedherein includes CDS in a dried form—i.e., the suspended fraction in thedried form as well as various fractions and variants of the suspendedfraction of stillage in the dried form, so that the components of DDSgenerally include the non-water components of CDS. DDS may be generallya powder, a granular material, or similar in various aspects.

In various aspects, the CDS may include components of the feedstock thatpass through the process units of the ethanol production facility, andmay also include waste yeast including yeast cells and/or portions ofyeast cells wasted from the process units. The CDS, in various aspects,includes oils, proteins, amino acids, non-fermented sugars, unconvertedstarches, unconverted cellulose, and other materials that may besensitive to heat and may oxidize, denature, or otherwise may be alteredby heat. The CDS, in various aspects, may include fiber, and may includeminerals such as phosphorous, sulfur, and calcium. The CDS may include,in various aspects, various additives such as buffers, acids, and/orbases for the adjustment/control of the pH and salts thereof, fillers,binding agents, and preservatives. The corresponding DDS would generallyinclude the non-water portions of the CDS such as, for example, oils,proteins, amino acids, non-fermented sugars, unconverted starches,unconverted cellulose, minerals, salts, binding agents, andpreservatives.

CDS may be obtained from an ethanol production facility configured toconvert starch-based biomass feedstock into ethanol. Such CDS includesthe generally suspended and/or solubilized non-fermentable components ofthe starch-based biomass feedstock. For example, the starch-basedbiomass may be grain such as corn. The grain includes starch as well asgerm, fiber, and gluten. The germ, fiber, and gluten in the grain may becommunicated through the process units of the ethanol productionfacility along with the starch as the starch is converted intofermentable sugar and the fermentable sugar is fermented into ethanol.Accordingly, the resulting CDS may generally include suspended and/orsolubilized non-fermentable materials in the grain feedstock such asgerm, fiber, and gluten, and may also include waste yeast, and may alsoinclude unfermented fermentable sugars and unconverted starch andoligosaccharides. The corresponding DDS would generally includecorresponding materials in substantially dried form in various aspects.

In other aspects, the germ, fiber, and/or gluten in the grain may beremoved by one or more process units prior to fermentation, and theresulting CDS may generally include the suspended and/or solubilizednon-fermentable portions of the grain feedstock that remain followingremoval of the germ, fiber, and/or gluten, as well as waste yeast andstarches that escaped conversion into sugar, and may also includeunfermented fermentable materials such as unfermented sugar. Thecorresponding DDS would generally include corresponding materials insubstantially dried form in various aspects.

In other aspects, CDS may be obtained from an ethanol productionfacility configured to convert cellulosic biomass feedstock intoethanol. Such CDS includes the generally suspended and/or solubilizednon-fermentable components of the cellulosic biomass feedstock. Thecorresponding DDS would generally include the generally suspended and/orsolubilized non-fermentable components of the cellulosic biomassfeedstock in substantially dried form in various aspects and may includeunconverted cellulose, various oligosaccharides, and/or unfermentedfermentable components.

Condensed distiller's solubles contains from about 12% to up to 50%solids. In some embodiments, CDS contains about 30-40% solids. Forexemplary purposes, CDS from High Plains Corporation was analyzed andthe results are shown in Tables 1 and 2. Total nitrogen, ammonia,phosphorus, protein and amino acids were analyzed using standardmethods. The content of major ethanol fermentation by-products,including lactate and acetate was also analyzed. The content of CDS canvary depending on the ethanol production process, grain used, includingcorn variety, growing season, and post processing methods.

TABLE 1 Characterization of Corn CDS Total Solids 28.7% Water 71.3%Total Nitrogen 1.20% Total Phosphorus 0.31% Crude Protein 7.30% Watersoluable peptides and amino acids 3.16% Ammonia 0.11% Lactate 2.40%Acetate 0.15%

TABLE 2 Characterization of Corn CDS from DGRA Dry Matter 33.4% CrudeProtein 20.8% Crude Fat 22.2% Crude Fiber 2.8% ADF 2.3% NDF 4.3% Ash9.2%

In general, CDS produced from a corn ethanol facility contains a highpercentage of fatty acids and oils from corn. The fatty acids areprimarily linoleic and oleic acids as well as other forms of fattyacids.

CDS has a shelf life of days before autooxidation occurs, resulting inrancidity, which negatively affects the product. Accordingly CDS isoften dried, using various methods, to produce dried distiller'ssolubles (DDS). Drying methods include processes using standard dryingequipment, including, without limitation, evaporation, spray drying,vented extrusion, belt drying, and pulse combustion drying. Some methodsand apparatus are described in U.S. patent application Ser. Nos.12/215,214 and 12/398,984, which are incorporated herein by reference intheir entireties. Drying CDS would generally preserve the solubles andsuspended material in CDS and may allow for storage and/or distribution.The DDS can be in the form of particles, powder, pellets, agglomeratesand other forms.

In other embodiments, other vegetable processed materials can also beused. By-products from other types of other alcohol processing canproduce material similar to CDS produced from corn ethanol production.Other alcohol processing includes, without limitation, production ofbeer, wine, sake, spirits and other alcohol processing. Various cerealgrains are used to produce alcohol products, including, withoutlimitation, rice, wheat, rye, corn, barley and other agriculturalinputs. In these applications, the cereal grains include variouspercentages of fatty acids, oils, proteins and amino acids thatrepresent byproduct streams from these processes. In these cases, theproteins, amino acids, oils and fatty acids also have been subjected tofermentation.

Another form of fatty acid/amino acid-protein by-product is in the formof soapstock. Soapstock is a by-product of soybean oil processing, inwhich soybeans are crushed and oil fatty acids are removed by hexaneextraction. The oils are refined and separated leaving a protein-aminoacid/fatty acid mixture, similar to CDS. In some embodiments, additionaloils, such as corn oil, used fryer waste oils, soybean oils, vegetableoils or other oils may be added to the mixture.

In other embodiments, co-products of biodiesel production may be used.By-products from the production of biodiesel from soybean oil and otheroils and/or fatty acid materials include, without limitation, forms ofglycerin, mixtures of fatty acids, oils proteins and/or amino acids andother materials.

DDS or CDS may be pretreated by chemical modification of proteins oramino acids in the material. CDS typically has a pH of about 4.Modifications can include, for example, treating proteins in CDS with anacid, base or other agent that alters the structure of one or more ofthe amino acid side chains, which, in turn, alters the character of theprotein and/or amino acids. For example, the high glutamine andasparagine of prolamines, particularly zein from corn, provides a meansfor manipulating the charge characteristics of the protein bydeamidation, thereby providing a wide range of hydrophobicity. In oneembodiment, deamidation involves mild acid catalyzed deamidation at a pHof about 1 at temperatures from about 25° C. to about 65° C. for aperiod of time sufficient to accomplish the desired level ofdeamidation. In some embodiments, acids that form stable dispersions andare useful within these classes include, without limitation, lacticacid, citric acid, malonic acid, phosphoric acid, fumaric acid, maleicacid, maleic anhydride, maleated propylenes, glutaric acid,transaconitic acid, acetic acid, propionic acid, sorbic acid, cysteineand glycyl glycine. In one embodiment, lactic acid in the form ofpolylactic acid is used. In another embodiment, maleated propylenes,such as G-3003 and G-3015 manufactured by Eastman chemicals are used.

Other examples of chemical modification include, without limitation,esterification of proteins with fatty alcohols and acylation of proteinswith fatty anhydrides.

Various materials may be added to DDS or CDS to form a DDS biocompositeadditive or additive for use in biopolymer compositions. The materialsinclude, without limitation, catalysts, fibers, cross-linkers, binders,proteins, natural biopolymers, minerals, impact modifiers, thermalstabilizers, lubricants, plasticizers, organic and inorganic pigments,biocides, processing aids, flame retardants, antioxidants, antistaticagents, delustering agents, coloring agents, aromatic agents, antiagingagents, fluorescent brightening agents, ultraviolet absorbers,ultraviolet stabilizers, slip additives, chain extenders, viscositystabilizers, emulsifiers, and other materials.

Various catalysts can be added to DDS, including, without limitation,metallic catalysts and non-metallic catalysts. Metal catalysts include,without limitation, metal oxides, including, for example, zinc oxide,titanium dioxide, copper oxides, (cuprous oxide and/or cupric oxide),aluminum oxide, calcium oxide, stannous oxide, lead oxide and othermetal oxides; and metals, for example, zinc, titanium, copper, iron,nickel, zirconium, and aluminum. Other catalysts include, withoutlimitation, fly ash and Portland cement.

Some oxides also assist with odor reduction and increase the shelf lifeof DDS. Without being bound by theory, oxides, such as titanium dioxide,may reduce autooxidation of CDS and DDS.

Plasticizers can be included in the DDS biocomposite additive, or can beadded to the thermoactive or thermoplastic material. Plasticizers canmodify the performance of the biopolymer, for example, by making it moreflexible and/or changing flow characteristics. The present biopolymercompositions can include plasticizer in amounts used in conventionalplastics. Suitable plasticizers include natural or synthetic compoundssuch as at least one of polyethylene glycol, polypropylene glycol,polyethylene-propylene glycol, triethylene glycol, diethylene glycol,dipropylene glycol, propylene glycol, ethylene glycol, glycerol,glycerol monoacetate, diglycerol, glycerol diacetate or triacetate,1,4-butanediol, diacetin sorbitol, sorbitan, mannitol, maltitol,polyvinyl alcohol, sodium cellulose glycolate, urea, cellulose methylether, sodium alginate, oleic acid, lactic acid, citric acid, sodiumdiethylsuccinate, triethyl citrate, sodium diethylsuccinate,1,2,6-hexanetriol, triethanolamine, polyethylene glycol fatty acidesters, oils, expoxified oils, natural rubbers, other knownplasticizers, mixtures or combinations thereof, and the like. Citrateesters, such as trimethyl citrate, triethyl citrate, tributyl citrate,trioctyl citrate, acetyltri-n-butyl citrate, acetyltriethyl citrate,acetyltri-n-hexylcitrate, butyryltri-n-hexyl citrate and the like mayalso be used as plasticizers. In certain embodiments, the present DDSbiocomposite additive and/or the biopolymer or can optionally includeabout 0.001 to about 15 wt-% plasticizer, about 0.001 to about 30 wt-%plasticizer, or about 0.001 to about 50 wt-% plasticizer.

Cross linking agents have been found to decrease the creep observed withplastic composite products and/or can modify water resistance.Crosslinking agents also have the ability to increase the mechanical andphysical performance of the present biopolymer. As used herein,crosslinking refers to linking the thermoactive material or plastic(s)and DDS or vegetable protein material. Crosslinking can be distinguishedfrom coupling agents which form bonds between plastic materials.Suitable crosslinking agents include one or more of metallic salts(e.g., NaCl or rock salt) and salt hydrates (which may improvemechanical properties), urea, formaldehyde, urea formaldehyde, ethylenevinyl acetate, (EVA), polyesters, phenol and phenolic resins, melamine,methyl diisocyanide (MDI), epoxides, other adhesive or resin systems,mixtures of combinations thereof, and the like. In an embodiment, thepresent biopolymer and/or DDS biocomposite additive can optionallyinclude about 0.001 to about 20 wt-% crosslinking agent. The same orsimilar agents may also serve as binders.

In some embodiments, the additive or biopolymer includes a lubricant. Alubricant can alter the fluxing or melting point in a compounding,extrusion or injecting molding process to achieve desired processingcharacteristics and physical properties.

Lubricants can be categorized as external, internal, andexternal/internal. These categories are based on the effect of thelubricant on the melt in a plasticizing screw or thermal kineticcompounding device as follows. External lubricants can provide goodrelease from metal surfaces and lubricate between individual particlesor surface of the particles and a metal part of the processingequipment. Internal lubricants can provide lubrication within thecomposition, for example, between resin particles, and can reduce themelt viscosity. Internal/external lubricants can provide both externaland internal lubrication.

Suitable external lubricants include non-polar molecules or alkanes,such as at least one of paraffin wax, mineral oil, polyethylene,mixtures or combinations thereof, and the like. Such lubricants can helpthe present biopolymer (for example, those including PVC) slip over thehot melt surfaces of dies, barrel, and screws without sticking andcontribute to the gloss on the end product surface. In addition anexternal lubricant can maintain the shear point and reduce overheatingof the biopolymer.

Suitable internal lubricants include polar molecules, such as at leastone of fatty acids, fatty acid esters, metal esters of fatty acids,mixtures or combinations thereof, and the like. Internal lubricants canbe compatible with thermoactive materials or plastics such as olefins,polyvinyl chloride (PVC), and other thermally active materials and DDSor vegetable protein material. These lubricants can lower meltviscosity, reduce internal friction and related heat due to internalfriction, and promote fusion.

Certain lubricants can also be natural plasticizers. Suitable naturalplasticizer lubricants include at least one of oleic acid, linoleicacid, polyethylene glycol, glycerol, stearic acid, palmitic acid, lacticacid, sorbitol, wax, epoxified oil (e.g., soybean), heat embodied oil,mixtures or combinations thereof, and the like.

Other lubricants include soapstock and other forms of byproduct fattyacids and/or oils. These include, without limitation, congealedvegetable oils, and other fatty acids or oils. The ability to use lowvalue byproducts from these agricultural processes creates a new valuefor these materials and supplies a solution to hazardous materials, thuscreating a sustainable solution. In some embodiments, the present DDSbiocomposite additive and/or biopolymer can optionally include about0.01 to about 10 wt-% lubricant.

The additive and/or biopolymer, in some embodiments, may include aprocessing aid. Suitable processing aids include acrylic polymers andalpha methylstyrene. These processing aids can be used with a PVCpolymer. A processing aid can reduce or increase melt viscosity andreduce uneven die flow. In a thermoactive and/or plastic material, itpromotes fluxing and acts like an internal lubricant. Increasing levelsof processing aids normally allow lower compounding, extrusion,injection molding processing temperatures. In some embodiments, thebiopolymer or DDS biocomposite additive can optionally include about 0.1to about 10 wt-% processing aid.

The additive and/or biopolymer may include an impact agent. Certainapplications require higher impact strength than a simple plastic.Suitable impact modifiers include acrylic, acrylonitrile-butadiene(ABS), acrylic copolymer, chlorinated polyethylene (CPE),methacryalate-butadiene-styrene (MBS), ethylene vinyl acetate (EVA),mixtures thereof, and the like. These impact modifiers can be used witha polyvinyl chloride (PVC) thermoactive material. In an embodiment, thepresent additive and/or biopolymer can optionally include about 0.1 toabout 10 wt-% impact modifier.

Fire retardants may also be added to the DDS biocomposite additiveand/or the biopolymer. Suitable fire retardants include, withoutlimitation, alumina trihydrate and magnesium hydroxide, which in someembodiments, are in the form of particles of about 40 microns indiameter or less. Phosphorous compounds, borates and zinc oxide may alsobe used as fire retardants. In an embodiment, the present additiveand/or biopolymer can optionally include about 0.001 to about 10 wt-%fire retardant.

The present additives and/or biopolymers can include a fiber additive.Suitable fibers include any of a variety of natural and syntheticfibers. Cellulose fibers include, without limitation, those from wood,agricultural fibers, including flax, hemp, kenaf, wheat, soybean,switchgrass, and grass, fibers obtained from paper and other fiberrecycling, including, without limitation, household and industrial paperrecycling streams, fibrous waste from the paper or wood industries,including paper mill sludge. Synthetic fibers include fiberglass,Kevlar, carbon fiber, nylon; mixtures or combinations thereof, and thelike. Mineral or silica additives may also be used. The fiber can modifythe performance of the biopolymers. For example, longer fibers can beadded to biopolymers structural members to impart higher flexural andrupture modulus. In some embodiments, the DDS biocomposite additive orbiopolymer can include about 0.001% to about 40% fiber.

Fillers may also be included in the DDS biocomposite additive and/or thebiopolymer. Examples of fillers include, without limitation, calciumcarbonate, magnesium carbonate, calcium hydroxide, calcium oxide,magnesium oxide, aluminum oxide, silicon oxide, iron oxide, boronnitride, titanium oxide, talc, pyrophyllite clay, silicate pigment,polishing powder, mica, sericite, bentonite, pearlite, zeolite,wollastonite, fluorite, dolomite, quick lime, slaked lime, kaolin,chlorite and diatomaceous earth.

Nanomaterials may also be used as fillers, including NanoCell (LDIComposites), which is a blend of cellulose, minerals and clay that hasbeen processed into a submicron material. It is derived from paper millsludge. NanoCell also contains small percentages of metals and titaniumdioxide. Other forms of nanomaterials, such as nanofibers, nanotubes,nanocellulosics, nanoclays and other forms of nanomaterials may also beincluded in the DDS biocomposite additive and/or the biopolymer.

Other materials that can be included in the present DDS biocompositeadditive and/or biopolymers can include components found in latex paint,including, without limitation, latex compounds, including, withoutlimitation, acrylic latexes such as styrenated acrylic latex; calciumcarbonate, colorants, dispersants, such as, for example, napthalenesulfonic acid condensation products; ammonium hydroxide; surfactants;glycol ethers, including (propylene glycol) methyl ether;2,2,4-trimethylpentanediol-1,3-monoisobutyrate; sodium nitrite; ethyleneglycols, such as triethylene glycol bis(2-ethylhexanoate); dryingagents, such as metal oxides, including, without limitation, zirconiumoxides, cobalt oxides and iron oxides, as well as ethylene oxides andethylene oxide derivatives and condensates, including, withoutlimitation, fatty alcohol ethoxylate, alkylphenol ethoxylate, fatty acidethoxylate, ethoxylated fatty amines, and the like; preservatives,emulsifiers and thickeners.

The DDS biocomposite additive may include DDS at about 30 to about 90wt-%.

The DDS biocomposite additive may be prepared by any of a variety ofmethods that can mix CDS or DDS with the other components. The methodsinclude compounding, which refers to putting together parts so as toform a whole, and/or forming by combining parts. Compounding methodsgenerally include wet compounding or dry compounding.

For wet compounding, condensed distiller's solubles (CDS) or drieddistiller's solubles is mixed with the other components, at least one ofwhich is in a solution. The solution may be generally liquid, syrup orother viscous fluid, or slurry, paste, or other non-Newtonian fluid, andthe CDS may include various agglomerations, aggregations,non-homogeneities, and/or clumps of material.

In some embodiments, the wet DDS biocomposite additive is dried. Dryingmethods include methods using standard drying equipment, including,without limitation, evaporation, spray drying, vented extrusion, beltdrying, and pulse combustion drying.

In some aspects, the wet compounded biocomposite additive is dried in adrying gas stream. Some methods and apparatus for drying the wetcompounded biocomposite additive are described in U.S. patentapplication Ser. Nos. 12/215,214 and 12/398,984, which are incorporatedherein by reference in their entireties.

In some aspects the wet compounded biocomposite additive is dried in adrying gas stream, and a particular embodiment of a pulse combustiondrier 30 is generally illustrated in FIG. 2A. The drying gas stream 20may consist generally of air and combustion products produced by thecombustion of various solid, liquid, or gaseous fuels or combinationsthereof. Examples of fuels would include propane, natural gas, andkerosene. In other aspects, the drying gas stream 20 may consist ofheated air or other gas propelled by the release of compression. Invarious aspects, the drying gas stream 20 may include other gases orcombinations of gases, which may be heated in various ways andconfigured to form the flowing drying gas stream 20, as would berecognized by those of ordinary skill in the art upon review of thisdisclosure.

In some aspects, the drying gas stream 20 may be characterized by agenerally continuous flow. In other aspects, the drying gas stream 20may be pulsed, and the pulses may have a frequency that may range fromabout 30 Hz to about 1,000 Hz. In various aspects, the drying gas stream20 may include regions of high velocity flow, turbulence, and mayinclude supersonic flows and shock waves. Pressures in the drying gasstream 20 may be about 2×104 Pa (gage) or more in various aspects. Soundpressures in the drying gas stream 20 may fall in the range of about 100dB to about 200 dB in various aspects. In various aspects, a swirlcomponent may be induced into the flow of the drying gas stream 20.

The flowing drying gas stream 20 defines a flow path 90 having a firstend 94 and a second end 96 with the drying gas stream 20 flowinggenerally from the first end 94 to the second end 96. The first end 94of the flow path 90 may be generally coincident with the location atwhich the drying gas stream 20 is generated. The second end 96 of theflow path 90 may be generally coincident with the region from which theDDS biocomposite additive is recovered from the drying gas stream 20 andmay be defined by various structures configured to recover the DDSbiocomposite additive. The wet compounded biocomposite additive may beintroduced into the flowing drying gas stream 20 at an introductionlocation 110, with the introduction location 110 disposed along the flowpath 90 generally between the first end 94 and the second end 96.

One or more passages 120, which may be defined by tubes, channels,pipes, or other structures, with each passage 120 having one or morepassage outlets 122 adapted for the introduction of the wet compoundedbiocomposite additive into the drying gas stream 20 may be located inthe flow path 90 between the first end 94 and the second end 96, and thelocation of the passage(s) 120 in the flow path 90 defines theintroduction location(s) 110. The wet compounded biocomposite additivemay be introduced into the drying gas stream 20 at the introductionlocation(s) 110 through the passage(s) 120. Pumps, piping, valves, andother such structures may be provided in various aspects to convey thewet compounded biocomposite additive to the passage(s) 120 forintroduction into the drying gas stream 20 at the introductionlocation(s) 110 as would be recognized by those of ordinary skill in theart upon review of this disclosure.

The temperature of the drying gas stream 20 may be 2,300° F. or moregenerally proximate the first end 94 of the drying gas stream 20, whichmay be excessive for drying the wet compounded biocomposite additive.Accordingly, the temperature of the drying gas stream 20 may becontrolled, in various aspects, to provide a first temperature 104generally proximate the introduction location 110 and/or a secondtemperature 106 generally proximate the second end 96 of the flow path90. The temperature of the drying gas stream 20 may be controlled invarious aspects to control the first temperature 104 of the drying gasstream 20 generally proximate the first end 94 of the flow path 90 wherethe wet DDS biocomposite additive may be introduced into the drying gasstream 20. The temperature of the drying gas stream 20 may be controlledin various aspects to control the second temperature 106 of the dryinggas stream 20 generally proximate the second end 96 of the flow path 90where the DDS biocomposite additive may be recovered from the drying gasstream 20.

For example, one or more gas flows may be combined with the drying gasstream 20 as the drying gas stream 20 flows along the flow path 90 tocontrol, at least in part, the first temperature 104 of the drying gasstream 20 at introduction location 110. The one or more gas flowscombined with the drying gas stream 20 may control, at least in part,the temperature at the second end 96 of the flow path 90. The one ormore gas flows combined with the drying gas stream 20 may control, atleast in part, the temperature variation between the first temperature104 and the second temperature 106. In various aspects, one or more gasflows may be combined with the drying gas stream 20 to provide for theuptake of water vapor and/or for other purposes as would be recognizedby those of ordinary skill in the art upon review of this disclosure. Invarious aspects, conditions at the first end 94 of the flow path 90 maybe adjusted in order to achieve a specific first temperature 104 and/orspecific second temperature 106.

The first temperature 104 and/or the second temperature 106 may bechosen depending upon the nature of the wet compounded biocompositeadditive to be introduced into the drying gas stream 20 in order to bedried into the DDS biocomposite additive. First and second temperatures104, 106 may be selected so that volatile organic content (VOC), whichmay contain valuable components, are not vaporized by high temperatures.For example, in various aspects, the first temperature 104 may rangefrom about 600° F. to about 2100° F. and the second temperature 106 mayrange from about 130° F. to about 200° F. In one embodiment, the firsttemperature 104 may be about 1,000° F. while the second temperature 106may be about 150° F. In other aspects, the first temperature 104 may beabout 600° F. to about 1200° F. and the second temperature 106 may beabout 130° F. to about 200° F. In another embodiment, the firsttemperature 104 may be about 1800° F. and the second temperature 106 maybe about 150° F. In yet another embodiment, the first temperature 104may be about 1200° F. and the second temperature 106 may be about 140°F.

The highly turbulent drying environment, due the high velocity of dryinggas stream 20, atomizes a viscous input, such as the wet compoundedbiocomposite additive, into smaller particles so that particles aredispersed. The high temperature gas stream 20 quickly evaporates thewater from the small particles. The highly turbulent environment allowsrapid mixing and communication between the hot drying gas stream 20 andthe atomized particles. The difference between the first and secondtemperatures 104, 106 of gas stream 20, ΔT, may be as large as 2000° F.In some aspects, ΔT ranges from 400° F. to about 1700° F. In someembodiments, ΔT is about 1650° F. Large ΔT allow for flash drying, infractions of seconds to milliseconds or less, so that the temperature ofdrying particles is never higher than approximately the secondtemperature 106. In some embodiments, drying of particles occurs in1/1000 to 1 second, including, without limitation, 1/1000, 1/100, 1/10,⅕, ¼, ⅓, ½, ⅔, ¾ seconds, or 1 second.

In some aspects, atomizing air, including, without limitation, gasdynamic atomizing is used to atomize the wet DDS biocomposite additive.In some embodiments, no spray nozzle is used. Using atomizing air todisperse the wet DDS biocomposite additive into droplets, has a numberof advantages over other drying methods, including spray drying. Ingeneral, spray dryers use either rotating disks or high pressurenozzles, which result in high shear forces. In contrast, gas or airatomization results in low or no shear forces. Pressures upstream of anatomizing venturi range from two to six psi above atmospheric pressure(14.7 psi). In addition, the hot air in conventional spray dryers isvery slow moving, and much less turbulent than pulse combustion dryinghot air. Accordingly, atomizing air at a very high first temperature, inconcert with a low second temperature, (i.e., high ΔT) results inextreme turbulence when a high velocity gas stream, which may be nearsonic velocity, is introduced into the drying chamber. This allows forvery rapid drying. Spray drying methods generally use much lower ΔT, andmuch lower gas velocity, resulting in little or no turbulence and muchlonger drying times. Longer drying times require much larger dryingchambers for spray drying, which increase capital costs dramatically.

The wet compounded biocomposite additive may be introduced into thedrying gas stream 20 at the introduction location 110 to be exposed tothe temperature of the drying gas stream 20 while being conveyed by thedrying gas stream 20 from the introduction location 110 to the secondend 96 of the flow path 90. The wet DDS biocomposite additive may beexposed to the temperature of the drying gas stream 20 for an exposuretime that may be on the order of fractions of a second, and, in someaspects, on the order of a millisecond or less. The temperature of thedrying gas stream 20 may cause water associated with the wet DDSbiocomposite additive to flash into the vapor phase, while the latentheat of vaporization of the water in combination with the exposure timemay keep the wet DDS biocomposite additive generally cool therebyprotecting the wet DDS biocomposite additive from the temperature ofdrying gas stream 20. Turbulence, high velocities, and/or shock waves inthe drying gas stream 20 may strip water from the wet DDS biocompositeadditive and may otherwise increase the rate of evaporation of waterfrom the wet DDS biocomposite additive by various mechanisms. The latentheat of evaporation of the water may also cool the drying gas stream 20,at least in part, from the first temperature 104 to the secondtemperature 106, so that the water content of the wet DDS biocompositeadditive may, in some aspects, control the second temperature 106 andmay control the temperature variation between the first temperature 104and the second temperature 106, at least in part. The rate at which wetDDS biocomposite additive is fed into the drying gas stream 20 maycontrol the first temperature 104, may control the second temperature106, and may control the form of the temperature gradient between thefirst temperature 104 and the second temperature 106.

In some aspects, the gas stream 20 has a maximum velocity of betweenabout 12,000 feet/minute (fpm) and about 50,410 fpm, (which translatesto velocities between about 61 meters/sec and 256 meters/sec), and insome embodiments maximum velocities are between about 24,000 fpm andabout 30,000 fpm (which translates to velocities between about 122meters/second and 153 meters/second), but may range upward intosupersonic velocities (67,000 fpm, or 343 meters/sec). When the flow ispulsed the gas stream 20 may oscillate between a lower value and themaximum velocity as will be recognized by those skilled in the art. Whenthe gas stream is continuous, the maximum velocity will be maintainedwithin a range or at a desired velocity within these ranges.

The high velocities result in extreme turbulence, which produces highheat transfer rates, leading to higher efficiency drying.

The evaporative rate may range from about 300 to about 600 pounds ofwater per hour in a dryer with a heat release of 1 million BTU per hour.The thermal efficiency may range from about 1200 to about 1800 BTU perpound of water removed. In some embodiments the thermal efficiency maybe about 1200 BTU per pound of water removed; in other embodiments, thethermal efficiency may be about 1300, 1400, 1500, 1600, 1700 or 1800 BTUper pound of water removed.

In some aspects, drying the wet compounded biocomposite additive to theDDS biocomposite additive may be a continuous process. In someembodiments using a large dryer, water from the wet DDS biocompositeadditive may be evaporated at a rate of about 10,000 pounds per hour toabout 50,000 pounds per hour.

A collector 60 may be positioned about the second end 96 of the flowpath 90 to recover the DDS biocomposite additive from the drying gasstream 20, and the collector 60 may generally define the second end 96of the flow path 90. The collector 60 may be a cyclone, baghouse, screenor series of screens, filter(s), or similar, or combinations thereofconfigured to capture the DDS biocomposite additive from the drying gasstream 20 as would be recognized by those of ordinary skill in the artupon review of this disclosure. The collector 60 may be configured tocooperate with various material handling and storage mechanisms for themanipulation and/or storage of DDS biocomposite additive, as would berecognized by those of ordinary skill in the art upon review of thisdisclosure.

In some aspects, the drying gas stream 20 may be generated by a pulsecombustion dryer 30. Examples of pulse combustion dryers 30 aredescribed in U.S. Pat. Nos. 3,462,995, 4,708,159, 4,819,873, and U.S.Pat. No. 4,941,820 to Lockwood, the disclosures of which areincorporated herein by reference in their entireties. The pulsecombustion dryer 30 may include a combustor 31 that defines a combustionchamber 32, and a tailpipe 40 that defines a tailpipe passage 42 havinga first tailpipe passage end 44 and a second tailpipe passage end 46.The tailpipe passage 42 is in fluid communication with the combustionchamber 32 through the first tailpipe passage end 44.

The pulse combustion dryer 30, in some aspects, may include a dryingchamber 50 that defines a drying chamber passage 52 having a firstdrying chamber passage end 54, a second drying chamber passage end 56,and centerline 153. The first drying chamber passage end 54 of thedrying chamber 50 may be disposed with respect to the second tailpipepassage end 46 of the tailpipe 40 so that the drying chamber passage 52is in fluid communication with the tailpipe passage 42, and, thence, influid communication with the combustion chamber 32. The combustor 31,tailpipe 40, and drying chamber 50 may be disposed with respect to oneanother in a variety of ways and may assume a variety of orientationswith respect to the vertical that would be readily recognized by thoseof ordinary skill in the art upon review of this disclosure.

Combustion air 86 and fuel 84 may be admitted into the combustionchamber 32, and the resulting fuel-air mixture ignited periodically toprovide the drying gas stream 20 in the form of a series of pulses ofair mixed with heated combustion products. Combustion of the fuel-airmixture may be generally complete so that the heated combustion productswould consist largely of carbon dioxide and water vapor. The drying gasstream 20 may flow from the combustion chamber 32, thru the tailpipepassage 42 from the first tailpipe passage end 44 to the second tailpipepassage end 46. In aspects that include the drying chamber 50, thedrying gas stream 20 may be communicated from the tailpipe passage 42into the drying chamber passage 52 generally proximate the first dryingchamber passage end 54, and the drying gas stream 20 may flow throughthe drying chamber passage 52 generally from the first drying chamberpassage end 54 to the second drying chamber passage end 56. Thus, theflow path 90 of the drying gas stream 20 includes the combustion chamber32, the tailpipe passage 42, and, in aspects that include the dryingchamber 50, the flow path 90 also generally includes the drying chamberpassage 52. The first end 94 of the flow path 90 may be generallycoincident with the combustion chamber 32.

In aspects wherein the drying gas stream 20 is generated by the pulsecombustion dryer 30, the collector 60 may be disposed generallyproximate the tailpipe passage second end 96 or, in aspects that includethe drying chamber 50, generally proximate the second drying chamberpassage end 56 to recover the DDS biocomposite additive. As would beunderstood by those of ordinary skill in the art upon review of thisdisclosure, the collector 60 may be disposed in other ways with respectto the drying chamber 50 to recover the DDS biocomposite additive fromthe second end 96 of the flow path 90 of the drying gas stream 20.

The wet compounded biocomposite additive may be introduced into thedrying gas stream 20 at the introduction location 110. In variousaspects, the introduction location 110 may be within the tailpipepassage 42 or within the drying chamber passage 52. The wet compoundedbiocomposite additive may be entrained in the drying gas stream 20generally at the introduction location 110 and dried into the DDSbiocomposite additive while being conveyed by the drying gas stream 20along the portion of the flow path 90 from the introduction location 110to the second end 96 of the flow path 90. The DDS biocomposite additivemay be recovered proximate the second end 96 of the flow path 90 of thedrying gas stream 20 by the collector 60.

The wet compounded biocomposite additive may be introduced into thedrying gas stream 20 at the introduction location 110 from one or morepassages 120 through one or more passage outlets 122 defined by the oneor more passages 120 disposed about the drying gas stream 20 at theintroduction location 110 for that purpose. The wet compoundedbiocomposite additive may pass through the one or more passages 120 intothe drying gas stream 20 by gravity feed and/or by the application ofpressures, which may be quite minimal. Pressure pulses in the drying gasstream 20 may aid in drawing the wet compounded biocomposite additivethrough the passage 120 and into the drying gas stream 20. Accordingly,the shear forces that the wet DDS biocomposite additive is subjected towhile passing through the passage 120 may be generally small ornegligible. In various aspects, the rate at which the wet compoundedbiocomposite additive is fed into the drying gas stream 20 may becontrollable.

In some aspects, nozzles, sprayers, or similar may be appended to thepassage 120 to disperse the wet compounded biocomposite additive fromthe passage outlet 122 into the drying gas stream 20. However, this maynot be necessary, as the velocity of the flow of the drying gas stream20 may be sufficient to disperse the wet DDS biocomposite additiveincluding the atomization of any agglomerations, aggregations,non-homogeneities and/or clumps of materials. The shock waves and/orturbulence in the drying gas stream 20 may disperse the wet compoundedbiocomposite additive. Sound waves in the drying gas stream 20 maysonicate the wet compounded biocomposite additive, which may aid in thedispersal of the wet DDS biocomposite additive into the drying gasstream 20. Pressure pulses in the drying gas stream 20 may also aid inthe dispersal of the wet compounded biocomposite additive into thedrying gas stream 20.

The embodiment of a pulse combustion dryer, shown in FIG. 2A includesthe combustor 31, the tailpipe 40 and the drying chamber 50. Asillustrated, the combustion chamber 31 fluidly communicates with thetailpipe passage 42 through the first tailpipe passage end 44. Thetailpipe 40, as illustrated, is disposed with respect to the dryingchamber 50 such that the tailpipe passage 42 fluidly communicatesthrough the second tailpipe passage end 46 into the drying chamberpassage 52 generally proximate the first drying chamber passage end 54.The collector 60 is disposed downstream of the second drying chamberpassage end 56, and the drying chamber passage 52 fluidly communicateswith the collector 60 through the second drying chamber passage end 56,as illustrated. In other embodiments, the collector 60 could beotherwise disposed with respect to the drying chamber 50. For example,at least a portion of the collector 60 could be positioned within aportion of the drying chamber passage 52 generally proximate the seconddrying chamber passage end 56.

In the embodiment illustrated in FIG. 2A, the drying gas stream 20 isgenerated within the pulse combustion dryer 30 and the wet DDSbiocomposite additive is introduced into the drying gas stream 20 to bedried into the DDS biocomposite additive. Fuel 84 and combustion air 86are admitted into the combustion chamber 32 defined by the combustor 31to be ignited periodically in order to produce the drying gas stream 20,as illustrated. An air valve 88 is disposed in the path of thecombustion air 88 in this embodiment to admit combustion air 86 into thecombustion chamber 32 while generally preventing backflows of the dryinggas stream 20. As illustrated in FIG. 2A, the flow of the drying gasstream 20 from the combustion chamber 32, through the tailpipe passage42, through the drying chamber passage 52 and into the collector 60defines the flow path 90. The first end 94 of the flow path 90 isgenerally within the combustion chamber 32, and the second end 96 of theflow path 90 is generally proximate the collector 60, which is disposedabout the second drying chamber passage end 56 of the drying chamber 50,in this embodiment.

The wet compounded biocomposite additive may be introduced into thedrying gas stream 20 at the introduction location 110 through thepassage outlet 122 defined by passage 120 in the embodiment illustratedin FIG. 2A. In this embodiment, a portion of the tailpipe 40 extendsinto the drying chamber passage 52 of the drying chamber 50, and theintroduction location 110 is within the drying chamber passage 52generally proximate the tailpipe passage second end 46 and generallyproximate the first drying chamber passage end 54. The passage 120 isdisposed within the drying chamber passage 52 to introduce the wetcompounded biocomposite additive into the drying gas stream 20 generallyproximate the centerline 153 of the drying chamber passage 52, asillustrated in FIG. 2A.

In other embodiments, a plurality of passages 120 may be provided andthese may define a plurality of introduction locations 110. One or morepassages 120 may be disposed within the drying chamber passage 42, insome embodiments, to introduce the wet compounded biocomposite additiveinto the drying gas stream 20 at an off-set from the centerline 153. Forexample, a plurality of passages 120 may be disposed circumferentiallywithin the drying chamber passage 42 with each passage 120 of theplurality of passages 120 positioned to introduce the wet compoundedbiocomposite additive into the drying gas stream 20 at a constant radiallocation with respect to the centerline 153.

As illustrated in FIG. 2A, the wet compounded biocomposite additive maybe introduced into the drying gas stream 20 through the passage outlet122 to be entrained into the drying gas stream 20 and dried into the DDSbiocomposite additive. The collector 60 is positioned proximate thesecond drying chamber passage end 56 and generally defines the secondend 96 of the flow path 90, in this illustrated embodiment. The DDSbiocomposite additive may then be recovered from the drying gas stream20 by the collector 60.

As illustrated in FIG. 2A, one or more additional airflows may beadmitted into the drying chamber passage 52 in various embodiments ofthe pulse combustion dryer 30. In the embodiment of FIG. 2A, quench air22 may be admitted into the drying chamber passage 52 generallyproximate the first drying chamber end 54 to control the temperature ofthe drying gas stream 20 within the drying chamber passage 52. Thequantity of quench air 22 admitted into the drying chamber passage 52may be regulated in order to control the temperature of the drying gasstream 20 including the first temperature 104 and the second temperature106. In this embodiment, dilution air 24 may also introduced into thedrying chamber passage 52 generally proximate the first drying chamberpassage end 54 to provide thermodynamic space for the uptake of waterevaporated from the wet compounded biocomposite additive in order toprevent water condensation and/or saturation conditions in the dryingchamber passage 52 and/or in the collector 60. The quantity of dilutionair 24 admitted into the drying chamber passage 52 may be regulated invarious embodiments.

As illustrated in FIG. 2A, the drying gas stream 20 may pass through acore region 155 generally proximate the centerline 153 of the dryingchamber passage 52. The dilution air 24 may pass through the wall region159 of the drying chamber passage 52, which is the portion of the dryingchamber passage 52 generally proximate the inner wall 53 of the dryingchamber 50. The quench air 22 may pass through an intermediate region157, which is intermediate between the wall region 159 and the coreregion 155.

The wet compounded biocomposite additive may be introduced into thedrying gas stream 20 passing though the core region 155. The quench air22 and/or the dilution air 24 may prevent or at least diminish contactbetween the wet DDS biocomposite additive/DDS biocomposite additive andthe inner wall 53 of the drying chamber 50 as the wet compoundedbiocomposite additive/DDS biocomposite additive is carried through thedrying chamber passage 42 by the drying gas stream 20 in order togenerally reduce or eliminate deposition of the DDS biocompositeadditive onto the inner wall 53.

FIG. 2B illustrates a cross-section of the embodiment of the dryingchamber 50 generally illustrated in FIG. 2A. As illustrated in FIG. 2B,the drying chamber 50 defines a drying chamber passage 52 having asubstantially circular cross-section. In this embodiment, the flows ofthe drying gas stream 20, the quench air 22, and the dilution air 24through the drying chamber passage 52 generally define three regionswithin the drying chamber passage. These three regions include the coreregion 155 generally proximate the centerline 153 through which thedrying gas stream 20 generally passes, the intermediate region 155through which the quench air 22 generally passes, and the wall region159 through which the dilution air 24 generally passes. The pulsecombustion dryer 30 may be configured to regulate the amount of quenchair 22 and/or the amount of dilution air 24 admitted into the dryingchamber passage 52 in order to regulate temperature and other conditionswithin the drying chamber passage 52. In other embodiments, one or moreairstreams could be introduced into the drying chamber passage 52 atvarious locations about the drying chamber passage 52 to cool the dryinggas stream 20, provide thermodynamic space for evaporation, or for otherpurposes as would be understood by those of ordinary skill in the artupon review of this disclosure.

The drying gas stream 20 has a first temperature 104 generally proximatethe introduction location 110, as illustrated in FIG. 2A. The drying gasstream 20 has a second temperature 106 generally proximate the secondend 96 of the flow path 90 of the drying gas stream 20, as illustrated.In various embodiments, the pulse combustion dryer 30 may be configuredto regulate the amount of additional gas flows such as the quench air 22and the dilution air 24 admitted into the drying gas stream 20 toregulate the temperature of the drying gas stream 20 including the firsttemperature 104 and the second temperature 106. In various embodiments,the admission of fuel into the combustion chamber 32 may be controlled,the pulse rate of the pulse combustion dryer 30 may be regulated, and/orthe pulse combustion dryer 30 may be configured and/or controlled inother ways to regulate the temperature of the drying gas stream 20including the first temperature 104 and the second temperature 106, aswould be recognized by those of ordinary skill in the art upon review ofthis disclosure. The temperature of the drying gas stream 20 includingthe first temperature 104 and the second temperature 106 may beadjusted, in various aspects, to produce the DDS biocomposite additivefrom the wet compounded biocomposite additive while not substantiallydenaturing proteins and/or oxidizing oils that may be present in the wetcompounded biocomposite additive/DDS biocomposite additive.

The DDS biocomposite additive prepared by wet compounding or mixingfollowed by pulse combustion drying may have the followingcharacteristics. The resulting particles may have a substantiallyuniform distribution of DDS biocomposite additive components andadditives within the particles. The moisture content may range fromabout 0.5% to about 15%.

In other aspects the DDS biocomposite additive may be prepared by drymixing or compounding, as illustrated in FIG. 1B. In this aspect, wetDDS biocomposite additive is dried to DDS biocomposite additive beforeadditional materials are added and mixed. To add additional materials tothe DDS, various methods for dry compounding can be used, and standardcompounding equipment, including co-rotational and counter rotationaltwin screws, extruders, thermal kinetic compounders, high shear mixers,paddle mixers, static mixers blenders and the like may be used. In oneaspect, the dry components are mixed together.

The DDS biocomposite additive may be in the form of, for example,pellets, particles granules, or powder. The powder obtained after dryingthe wet compounded biocomposite additive to the DDS biocompositeadditive may be processed further, for example, into pellets usingstandard industrial pelletizing equipment, or may be processed, forexample, into granules, using standard industrial granulation equipment.

In some embodiments, the DDS biocomposite additive may comprise separatecomponents, such as DDS separate from other additives, so that thecomponents are added separately to the plastic or thermoactive material.

In some aspects, the DDS biocomposite additive comprises drieddistiller's solubles, a metal oxide, and a fiber. In some embodiments,the DDS biocomposite additive comprises dried distiller's solubles, ametal oxide, a fiber and latex. The latex may be any number of latexcompounds, including, without limitation, latex, acrylic latex, acryliclatex compounds, including, without limitation styrenated acrylic latex.In some embodiments, the DDS biocomposite additive comprises drieddistiller's solubles, a metal oxide, a fiber and white latex paint.White latex paint may include latex as well as a number of othercomponents described above. The fiber may be a cellulose fiber or otherfibers described above. The cellulose fiber may be paper mill sludge orfiber obtained from other paper recycling. In some embodiments, the DDSbiocomposite also comprises a drying agent found in latex paint,including, without limitation, a metal oxide, such as zirconium oxide,copper oxide, cobalt oxide and/or iron oxide, and/or an ethylene oxidederivative or condensate. In some embodiments the DDS comprises about0.01 wt-% to about 1 wt-% of an oxide drying agent.

In some aspects the DDS biocomposite additive comprises about 30 wt-% toabout 90 wt-% dried distiller's solubles, about 2 wt-% to about 20 wt-%metal oxide, about 5 wt-% to about 50 wt-% fiber and about 1 wt-% toabout 15 wt-% latex or a latex derivative or compound. In someembodiments, the dried distiller's solubles is obtained from a cornethanol production facility. In some embodiments, the metal oxide istitanium oxide or zinc oxide, or a combination thereof. In otheraspects, the DDS biocomposite additive comprises about 40 wt-% to about80 wt-% dried distiller's solubles, about 3 wt-% to about 15 wt-% metaloxide, about 10 wt-% to about 40 wt-% fiber and about 2 wt-% to about 10wt-% latex or a latex derivative or compound. In yet other aspects, theDDS biocomposite additive comprises about 50 wt-% to about 70 wt-% drieddistiller's solubles, about 5 wt-% to about 10 wt-% metal oxide, about15 wt-% to about 35 wt-% fiber and about 3 wt-% to about 7 wt-% latex ora latex derivative or compound. In even other aspects, the DDSbiocomposite additive comprises about 55 wt-% to about 65 wt-% drieddistiller's solubles, about 7 wt-% to about 9 wt-% metal oxide, about 20wt-% to about 30 wt-% fiber and about 4 wt-% to about 6 wt-% latex or alatex derivative or compound. In some embodiments, the DDS is obtainedfrom wet DDS biocomposite additive, which was produced in a corn ethanolproduction facility, the metal oxide is titanium dioxide, the fiber iscellulose fiber and the latex compound is latex or styrenated acryliclatex. In some embodiments, the cellulose fiber is obtained from papermill sludge or from a paper recycling stream. In one embodiment, the DDSbiocomposite additive comprises 61 wt-% dried distiller's solubles, 7wt-% titanium dioxide, 25 wt-% cellulose and 7 wt-% latex paint solids.In another embodiment, the DDS biocomposite additive comprises 61 wt-%dried distillers solubles, 8 wt-% titanium dioxide, 25 wt-% celluloseand 5 wt-% latex, acrylic latex or styrenated acrylic latex.

In some aspects the invention provides a DDS biocomposite additiveprepared by combining a mixture comprising about 30 wt-% to about 90wt-% dried distiller's solubles, about 5 wt-% to about 20 wt-% metaloxide, and about 5 wt-% to about 50 wt-% fiber, drying the mixture in apulsed drying gas stream. The pulsed gas stream may be generated by apulse combustion dryer. The DDS biocomposite additive may also beprepared by the above method with the addition of from about 1 wt-% toabout 15 wt-% latex, acrylic latex, or styrenated acrylic latex in themixture.

In addition to the DDS biocomposite additive, the biopolymer of thepresent invention can include any of a wide variety of plastic and/orthermoactive materials. In some embodiments, the thermoactive and/orplastic material can be selected for its ability to form a homogeneousor largely homogeneous dough, including the DDS biocomposite additive.In some embodiments, the thermoactive and/or plastic material can beselected for its ability to covalently bond with the DDS biocompositeadditive. In some or other embodiments, the thermoactive and/or plasticmaterial can be selected for its ability to flow when mixed orcompounded with the DDS biocomposite additive. In some or otherembodiments, the thermoactive and/or plastic material can set afterbeing formed. Numerous such thermoactive and/or plastic materials arecommercially available.

Suitable thermoactive and/or plastic materials include thermoplastic,thermoset material, a resin and adhesive polymer, and the like. As usedherein, the term “thermoplastic” refers to a plastic that can oncehardened be melted and reset. As used herein, the term “thermoset”material refers to a material (e.g., plastic) that once hardened cannotreadily be melted and reset. As used herein, the phrase “resin andadhesive polymer” refers to more reactive or more highly polar polymersthan thermoplastic and thermoset materials.

Suitable thermoplastics include polyamide, polyolefin (e.g.,polyethylene, polypropylene, poly(ethylene-copropylene),poly(ethylene-coalphaolefin), polybutene, polyvinyl chloride, acrylate,acetate, and the like, polystyrenes (e.g., polystyrene homopolymers,polystyrene copolymers, polystyrene terpolymers, and styreneacrylonitrile (SAN) polymers, polysulfone, halogenated polymers (e.g.,polyvinyl chloride, polyvinylidene chloride, polycarbonate, and thelike, copolymers and mixtures of these materials, and the like. Suitablevinyl polymers include those produced by homopolymerization,copolymerization, terpolymerization, and like methods. Suitablehomopolymers include polyolefins such as polyethylene, polypropylene,poly-I-butene, and the like, polyvinylchloride, polyacrylate,substituted polyacrylate, polymethacrylate, polymethylmethacrylate,copolymers, mixtures of these materials, and the like. Suitablecopolymers of alpha-olefins include ethylene-propylene copolymers,ethylene-hexylene copolymers, ethylene-methacrylate copolymers,ethylene-methacrylate copolymers, copolymers and mixtures of thesematerials, and the like. In certain embodiments, suitable thermoplasticsinclude polypropylene (PP), polyethylene (PE), and polyvinyl chloride(PVC), copolymers and mixtures of these materials, and the like. Incertain embodiments, suitable thermoplastics include polyethylene,polypropylene, polyvinyl chloride (PVC), low density polyethylene(LDPE), copoly-ethylenevinyl acetate, copolymers and mixtures of thesematerials, and the like.

Suitable thermoset materials include epoxy materials, melaminematerials, copolymers and mixtures of these materials, and the like. Incertain embodiments, suitable thermoset materials include epoxymaterials and melamine materials. In certain embodiments, suitablethermoset materials include epichlorohydrin, bisphenol A, diglycidylether of 1,4-butanediol, diglycidyl ether of neopentyl glycol,diglycidyl ether of cyclohexanedimethanol, aliphatic; aromatic aminehardening agents, such as triethylenetetraamine, ethylenediamine,N-cocoalkyltrimethylenediamine, isophoronediamine,diethyltoluenediamine, tris(dimethylaminomethylphe-nol); carboxylic acidanhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalicanhydride, maleic anhydride, polyazelaic polyanhydride and phthalicanhydride, mixtures of these materials, and the like.

Suitable resin and adhesive polymer materials include resins such ascondensation polymeric materials, vinyl polymeric materials, and alloysthereof. Suitable resin and adhesive polymer materials includepolyesters (e.g., polyethylene terephthalate, polybutyleneterephthalate, and the like), methyl diisocyanate (urethane or MDI),organic isocyanide, aromatic isocyanide, phenolic polymers, urea basedpolymers, copolymers and mixtures of these materials, and the like.Suitable resin materials include acrylonitrile-butadiene-styrene (ABS),polyacetyl resins, polyacrylic resins, fluorocarbon resins, nylon,phenoxy resins, polybutylene resins, polyarylether such aspolyphenylether, polyphenylsulfide materials, polycarbonate materials,chlorinated polyether resins, polyethersulfone resins, polyphenyleneoxide resins, polysulfone resins, polyimide resins, thermoplasticurethane elastomers, copolymers and mixtures of these materials, and thelike. In certain embodiments, suitable resin and adhesive polymermaterials include polyester, methyl diisocyanate (urethane or MDI),phenolic polymers, urea based polymers, and the like.

Suitable thermoactive materials include polymers derived from renewablesources, such as polymers including polylactic acid (PLA) and a class ofpolymers known as polyhydroxyalkanoates (PHA). PHA polymers includepolyhydroxybutyrates (PHB), polyhydroxyvalerates (PHV), andpolyhydroxybutyrate-hydroxyvalerate copolymers (PHBV), polycaprolactone(PCL) (i.e. TONE), polyesteramides (i.e., BAK), a modified polyethyleneterephthalate (PET) (i.e., BIOMAX), and “aliphatic-aromatic” copolymers(i.e, ECOFLEX and EASTAR BIO), mixtures of these materials and the like.The biopolymer can contain from about 1% to about 50% of polymersderived from renewable sources, such as PLA and PHAs.

Other suitable thermoactive materials include thermoplastic elastomers,such as thermoplastic polyurethanes, vulcanized thermoplasticpolyolefins, thermoplastic vulcanizate, polyolefin elastomers, and thelike. Suitable thermoplastic polyurethane can be or include an aromaticpolyester based thermoplastic polyurethane. Such thermoplasticpolyurethanes are commercially available under the tradenames TEXIN®(e.g., TEXIN® 185) or DESMOPAN® from Bayer. Suitable thermoplasticelastomers are known and commercially available from any of a variety ofsources. Suitable thermoplastic elastomers include thermoplasticvulcanizate sold under the tradename SARLINK® and the thermoplasticvulcanizate sold under the tradename SANTOPRENE.

Suitable thermoactive materials include terephthalate polymers, such aspoly(trimethylene terephthalate) and polybutylene terephthalate (PBT).These thermoactive materials can include, for example, monomeric unitsderived from dimethylterephthalate (DMT) and/or terephthalic acid (TPA)and also 1,3-propanediol or 1,4-butanediol. Suitable thermoactivematerials include other diol derived polymers, for example, polyesterssuch as poly(butylene adipate) diols, which can be formulated intourethane elastomers.

Thermoactive materials, or thermoplastic materials can include mixturesof recycled plastics. Recycled plastics from a variety of sources may beused. For example, plastic may be obtained from plastic waste including,without limitation, grocery bags, agricultural films, plastic sheets,disposable cups, plates, containers, industrial scrap and municipalwaste, including plastics recovered from household recycling programs,from plastic recycling centers and from various sectors of industry, andfrom waste electrical and electronic equipment. The recycled plasticscan include, without limitation, homopolymers or copolymers of ethylene,polypropylene, vinyl chloride, styrene, acrylonitride, butadiene,acrylic acid, methacrylic acid, methylacrylate, methylmethylacrylate,acrylamide, carbonates, polybutylene, terephthalate, polyethylenenaphthalate, cellulose acetate, cellulose acetate butryrate, polyacetal,poly(vinyl butyral) polyurethane and mixtures thereof. The plastics maybe shredded, densified, granulated or regrind. In some embodiments, therecycled plastic has a meltable plastic portion of at least 50%.

In some embodiments, the biopolymer can include thermoactive or plasticmaterial at about 0.01 to about 95 wt-%, about 1 to about 95 wt-%, about5 to about 30 wt-%, about 5 to about 40 wt-%, about 5 to about 50 wt-%,about 5 to about 85 wt-%, about 5 to about 95 wt-%, about 10 to about 30wt-%, about 10 to about 40 wt-%, about 10 to about 50 wt-%, or about 10to about 95 wt-%. In certain embodiments, the biopolymer can includethermoactive material at about 95 wt-%, about 75 wt-%, about 50 wt-%,about 45 wt-%, about 40 wt-%, about 35 wt-%, about 30 wt-%, about 25wt-%, about 20 wt-%, about 15 wt-%, about 10 wt-%, or about 5 wt-%. Thepresent biopolymer can include any of these amounts or ranges notmodified by about.

Thermoplastic, thermoset, resin and/or adhesive polymer materials may becompounded or mixed with the DDS biocomposite additive using any of avariety of methods. Other additives may also be compounded with thethermoplastic or thermoactive material and the DDS biocompositeadditive.

Compounding can include heating the DDS biocomposite additive and thethermoplastic, thermoset, resin and/or adhesive polymer materials.Compounding can include extruding, high shear mixing and the like. Thecompounded biopolymer can be used directly or can be formed as pellets,granules or other convenient form for converting to articles by moldingor other processes. Advantageously, the compounded DDS biocompositeadditive and the thermoplastic, thermoset, resin and/or polymer adhesivematerial can be an integrated mass that homogenous or nearly so.

The present biopolymer can be formed by any of a variety of extrudingprocesses suitable for mixing or compounding the DDS biocompositeadditive and the thermoplastic, thermoset, resin and/or polymer adhesivematerial. For example, conventional extruding processes, such as twinscrew compounding, can be employed to make the present biopolymer.Compounding by extruding can provide a higher internal temperaturewithin the extruder and promote the interaction of the thermoplastic,thermoset, resin and/or polymer adhesive material with the DDSbiocomposite additive. Twin screw compounding can employ co- orcounter-rotating screws. The extruder can include vents that allowescape of moisture or volatiles from the mixture being compounded. Usinga die on the extruder can compound and form the biopolymer.

In some aspects the biopolymer includes about 60 wt-% to about 99.5 wt-%of a thermoplastic, thermoset, resin, polymer adhesive material, ormixtures thereof and about 0.5 wt-% to about 40 wt-% of the DDSbiocomposite additive. In other embodiments, the biopolymer includesabout 80 wt-% to about 99.5 wt-% of a thermoplastic, thermoset, resin,polymer adhesive material, or mixtures thereof and about 0.5 wt-% toabout 20 wt-% of the DDS biocomposite additive. In even otherembodiments, the biopolymer includes about 99, 98, 97, 96, 95, 94, 93,92, 90, 88, 85, or 80 wt-% of a thermoplastic, thermoset, resin, polymeradhesive material, or mixtures thereof and about 1, 2, 3, 4, 5, 6, 7, 8,10, 12, 15, or 20 wt-%, respectively, of the DDS biocomposite additive.

In some aspects, the biopolymer includes about 60 wt-% to about 99.5wt-% of a thermoplastic, thermoset, resin, polymer adhesive material, ormixtures thereof; about 0.15 wt-% to about 35 wt-% of DDS, about 0.025wt-% to about 8.0 wt-% of a metal oxide, and about 0.025 wt-% to about 8wt-% of fiber. The metal oxide can be any of the metal oxides describedabove, and in some embodiments the metal oxide is titanium dioxide, zincoxide or mixtures thereof. In some embodiments, the fiber is a cellulosefiber. In some embodiments the biopolymer includes about 80 wt-% toabout 99.5 wt-% of a thermoplastic, thermoset, resin, polymer adhesivematerial, or mixtures thereof; about 0.15 wt-% to about 20 wt-% of DDS,about 0.025 wt-% to about 4.0 wt-% of a metal oxide, and about 0.025wt-% to about 4 wt-% of fiber. In some embodiments the biopolymer alsoincludes about 0.005 wt-% to about 6 wt-% latex, or latex compounds,including, without limitation, acrylic latex and/or styrenated acryliclatex. In some embodiments, the biopolymer includes about 99 wt-% of athermoplastic, thermoset, resin, polymer adhesive material, or mixturesthereof; about 0.3 wt-% to about 0.9 wt-% of DDS, about 0.02 wt-% toabout 0.2 wt-% of a metal oxide, about 0.05 wt-% to about 0.2 wt-% offiber and about 0.01 wt-% to about 0.15 wt-% of latex, acrylic latex orstyrenated acrylic latex. In other embodiments, the biopolymer includesabout 95 wt-% of a thermoplastic, thermoset, resin, polymer adhesivematerial, or mixtures thereof; about 1.5 wt-% to about 4.5 wt-% of DDS,about 0.1 wt-% to about 1 wt-% of a metal oxide, about 0.25 wt-% toabout 1 wt-% of fiber and about 0.05 wt-% to about 0.75 wt-% of latex,acrylic latex or styrenated acrylic latex. In other embodiments, thebiopolymer includes about 95 wt-% of a thermoplastic, thermoset, resin,polymer adhesive material, or mixtures thereof; about 2 wt-% to about 4wt-% of DDS, about 0.2 wt-% to about 0.6 wt-% of a metal oxide, about0.5 wt-% to about 2 wt-% of fiber and about 0.2 wt-% to about 0.6 wt-%of latex, acrylic latex or styrenated acrylic latex. In otherembodiments, the biopolymer includes about 90 wt-% of a thermoplastic,thermoset, resin, polymer adhesive material, or mixtures thereof; about3 wt-% to about 9 wt-% of DDS, about 0.2 wt-% to about 2 wt-% of a metaloxide, about 0.5 wt-% to about 2 wt-% of fiber and about 0.1 wt-% toabout 1.5 wt-% of latex, acrylic latex or styrenated acrylic latex. Inother embodiments, the biopolymer includes about 90 wt-% of athermoplastic, thermoset, resin, polymer adhesive material, or mixturesthereof; about 4 wt-% to about 6 wt-% of DDS, about 0.4 wt-% to about1.2 wt-% of a metal oxide, about 1.0 wt-% to about 4 wt-% of fiber andabout 0.2 wt-% to about 1 wt-% of latex, acrylic latex or styrenatedacrylic latex. In other embodiments, the biopolymer includes about 80wt-% of a thermoplastic, thermoset, resin, polymer adhesive material, ormixtures thereof; about 6 wt-% to about 18 wt-% of DDS, about 0.4 wt-%to about 4 wt-% of a metal oxide, about 1.0 wt-% to about 4 wt-% offiber and about 0.2 wt-% to about 3 wt-% of latex, acrylic latex orstyrenated acrylic latex. In other embodiments, the biopolymer includesabout 80 wt-% of a thermoplastic, thermoset, resin, polymer adhesivematerial, or mixtures thereof; about 8 wt-% to about 12 wt-% of DDS,about 0.8 wt-% to about 2.4 wt-% of a metal oxide, about 2 wt-% to about8 wt-% of fiber and about 0.4 wt-% to about 2 wt-% of latex, acryliclatex or styrenated acrylic latex. In some embodiments the metal oxideincludes titanium dioxide. In some embodiments the fiber includescellulose fiber. In some embodiments, the thermoplastic is polyvinylchloride, polyethylene, polypropylene, HDPE, LDPE, or mixtures thereof.In other embodiments the thermoplastic is recycled plastic, with ameltable portion of at least 50%. In some embodiments, the biopolymeralso includes about 0.001 wt-% to about 1 wt-% of ethylene oxidederivatives.

The present biopolymer can be suitable for forming (e.g., by extrudingor molding) into a myriad of forms and end products. For forming, thebiopolymer can be in any of a variety of forms, such as particles,granules, or pellets. Articles, such as bars, sheet stock, or otherformed articles can be produced from the present biopolymer through anyof a variety of common, known manufacturing methods including extrusionmolding, injection molding, blow molding, compression molding, transfermolding, thermoforming, casting, calendering, low-pressure molding,high-pressure laminating, reaction injection molding, foam molding, andcoating. For example, the present biopolymer can be formed into articlesby injection molding, extrusion, compression molding, other plasticmolding processes, or with a robotically controlled extruder such as amini-applicator. The present biopolymer including the DDS biocompositeadditive can be used in, for example, paints, adhesives, coatings,powder coatings, plastics, polymer extenders, and the like.

The DDS biocomposite additive can be used in a variety of applications,including, without limitation, as a foaming agent, as an agent to lowerthe Tm or Tg of a thermoplastic, thermoset, resin and/or polymeradhesive material, and/or as a compatibilizing agent for mixtures ofthermoplastic, thermoset, resin and/or polymer adhesive materials.

In one aspect the DDS biocomposite additive can act as a foaming agent.When added to a thermoplastic material, such as high densitypolyethylene, low density polyethylene, polypropylene, polystyrene,polycarbonate, ethylene vinylacetate, polylactic acid,polyhydroxyalkanoates, metallocene, polyvinyl chloride, and the like,the resulting biopolymer can be foamed, either from a soft form or uponmelting, without addition of other foaming or blowing agents. Thethermoplastic-DDS biocomposite additive can foam upon extruding, or whenused in molding processes, including injection molding. In injectionmolding, the mold can be partially filled to allow the foaming action ofthe biopolymer to fill the cavity.

Without being bound by theory, it is thought that as the proteins in DDSare blended, heated, sheared and under pressure, they release carbondioxide and/or nitrogen as the proteins uncoil and become more polar.The carbon dioxide and/or nitrogen becomes saturated within the moltenpolymer under pressure. When subjected to a pressure drop, the carbondioxide comes out of solution to create microbubbles starting fromnucleating sites of the micro- or nano-fiber or protein particles.

In some aspects, the resulting foamed biopolymer has an interior foamedmaterial and a non-foam shell.

The DDS biocomposite additive when used as a foaming agent has a numberof advantages, including, reduction in the amount of thermoplasticmaterial needed through component density reduction, thinner design andmaterial substitution, reduced equipment costs through the purchase ofsmaller and fewer machines, and fewer and less expensive molds, reducedoperating costs through cycle time reductions of up to 50%, reducedscrap rates and lower energy consumption, and the ability to moldthermoplastic parts that are flatter, straighter and dimensionallyimproved. In some embodiments, the amount of thermoplastic materialsused is reduced from about 20% to about 50%. In one embodiment, theamount of thermoplastic materials used is reduced about 30%.

The present invention also includes a foamed biopolymer compositionprepared by combining a mixture comprising about 80 wt-% to about 99.5wt-% of a thermoplastic material, about 0.15 wt-% to about 10 wt-% ofDDS, about 0.025 wt-% to about 4.0 wt-% of a metal oxide; and about0.025 wt-% to about 10 wt-% of fiber; and forming the foamed compositionby extruding or molding the mixture. The mixture may further compriseabout 0.005 wt-% to about 6 wt-% latex, acrylic latex, other latexcompound or mixtures thereof. In other embodiments, the mixture may alsocomprise about 0.001 wt-% to about 1 wt-% of ethylene oxide derivatives.In some embodiments, the thermoplastic material is HDPE, and in otherembodiments the thermoplastic material is a combination of HDPE andpolypropylene.

The DDS biocomposite additive can also act to lower the melting andextrusion temperatures of thermoplastic, thermoset, resin and/or polymeradhesive materials and mixtures thereof. In some aspects, a biopolymercomposition comprising one or more thermoplastic materials and the DDSbiocomposite additive can be processed at a temperature of about 10 toabout 35% below the processing temperature without the addition of theDDS biocomposite additive. Such a biopolymer comprises about 80 wt-% toabout 99.5 wt-% of a thermoplastic, thermoset, resin, polymer adhesivematerial, or mixtures thereof; about 0.15 wt-% to about 10 wt-% of DDS,about 0.025 wt-% to about 4.0 wt-% of a metal oxide, and about 0.025wt-% to about 10 wt-% of fiber.

The present invention also provides a biopolymer composition prepared bycombining a mixture comprising about 80 wt-% to about 99.5 wt-% of athermoplastic, or thermoplastic mixture, about 0.15 wt-% to about 10wt-% of DDS, about 0.025 wt-% to about 4.0 wt-% of a metal oxide andabout 0.025 wt-% to about 10 wt-% of fiber; and processing the mixtureat a temperature about 10% to about 35% below the processing temperatureof the thermoplastic alone or thermoplastic mixture alone. The mixturemay further comprise about 0.005 wt-% to about 6 wt-% latex, acryliclatex, other latex compound or mixtures thereof. In other embodiments,the mixture may also comprise about 0.001 wt-% to about 1 wt-% ofethylene oxide derivatives.

The DDS biocomposite additive may also act as a compatibilizing additivefor incompatible plastics, including post consumer comingled recycledplastic. The mixed plastics can include a mixture of thermoplasticmaterials. In some aspects, the addition of a DDS biocomposite additiveto a mixture of incompatible thermoplastics allows the incompatiblethermoplastic constituents of the mixture to combine into a singlehomogeneous mass. The recycled plastics can include a number ofthermoplastic materials, including, without limitation, styrene,olefins, polyvinyl chloride, and other thermoplastics. When incompatibleplastics are mixed, and processed through an extruder, the resultingmaterial is not homogeneous, and contains unmixed sections anddiscontinuities. In some embodiments, a biocomposite mixture includesabout 80 wt % to about 99 wt % of the thermoplastic mixture, and about 1wt % to about 20 wt % of the DDS biocomposite additive. When thisbiocomposite mixture is processed using an extruder, the extrudedmaterial becomes homogeneous.

The present invention also provides a biopolymer composition prepared bycombining a mixture comprising about 80 wt-% to about 99.5 wt-% of amixture of incompatible thermoplastic materials, about 0.15 wt-% toabout 10 wt-% of DDS, about 0.025 wt-% to about 4.0 wt-% of a metaloxide; and about 0.025 wt-% to about 10 wt-% of fiber; and forming thehomogeneous thermoplastic composition by extruding the mixture. Themixture may further comprise about 0.005 wt-% to about 6 wt-% latex,acrylic latex, other latex compound or mixtures thereof. In otherembodiments, the mixture may also comprise about 0.00 wt-% to about 1wt-% of ethylene oxide derivatives. The incompatible thermoplastics caninclude any of a number of recycled plastics obtained from differentsources. In some embodiments, the recycled plastic mixture includes atleast 50% meltable plastic.

The present invention also provides a method of recycling mixedthermoplastics by combining a mixture comprising about 80 wt-% to about99.5 wt-% of a mixture of incompatible thermoplastic materials, about0.15 wt-% to about 10 wt-% of DDS, about 0.025 wt-% to about 4.0 wt-% ofa metal oxide; and about 0.025 wt-% to about 10 wt-% of fiber; andforming the homogeneous thermoplastic composition by extruding ormolding the mixture. The mixture may further comprise about 0.005 wt-%to about 6 wt-% latex, acrylic latex, other latex compound or mixturesthereof. In other embodiments, the mixture may also comprise about 0.001wt-% to about 1 wt-% of ethylene oxide derivatives. The incompatiblethermoplastics can include any of a number of recycled plastics obtainedfrom different sources. In some embodiments, the recycled plasticmixture includes at least 50% meltable plastic.

EXAMPLES

A further understanding may be obtained by reference to certain specificexamples, which are provided herein for the purpose of illustration onlyand are not intended to be limiting unless otherwise specified.

Example 1 Production of DDS Biocomposite Thermoplastic by PulseCombustion Drying Condensed Distiller's Solubles with Additives

Condensed distiller's solubles (CDS) was obtained from an operating cornethanol facility. The measured solids concentration in the material was32% and it had the appearance of a thick viscous liquid. The liquid wascombined with cellulose fibers obtained from a paper recycling stream,industrial grade titanium dioxide, and white latex paint. After drying,the mixing formula of ingredients was 61% dry weight DDS, 25% cellulosefiber, 7% titanium dioxide, and 7% white latex paint solids.

This liquid mixture was introduced into a P-1 Pulse Combustion Drier(Pulse Combustion Systems, Payson, Ariz.) using an impeller pump. Thedrier was operated at 800,000 Btu per hour heat release and an exittemperature of 180° F. The liquid mixture dried into a light tan powderwith residual moisture content of less than 5%. This powder is oneformulation of DDS biocomposite additive. It can be used either as thepowder or processed further into pellets using standard industrialpelletizing equipment, or granules, using standard industrialgranulation equipment.

Example 2 DDS Biocomposite Additive Used as a Compatiblizing Additivewith Post Consumer Comingled Recycled Plastic

A supply of post consumer comingled recycled plastic (PCCRP) wasobtained from a plastics recycling line. The materials were estimated tocontain approximately 50% styrene mixed with olefins, PVC and otherunknown plastics that occur in the stream. The recommended processingtemperature for extrusion of this thermoplastic mix was 450° F.

A single screw thermoplastic extruder with a 2 inch barrel was used toconduct trial extrusions through a rectangular die into a water coolingbath and out of the bath through a puller used to keep the extrudedmaterial taut. The extruder was preheated to 450° F. and PCCRC with noaddition was loaded into the feed hopper. The material emerged from thedie in strings with obvious unmixed sections and discontinuities. PCCRCwith a 5% addition of the DDS Biocomposite Additive, as described inExample 1, was fed into the extruder. The material emerged intact with ahomogenous appearance. The addition of the DDS biocomposite additive, asdescribed in Example 1, allowed the incompatible thermoplasticconstituents of the mixture to combine into a single homogeneous mass.

Example 3 Reduction in Processing Temperatures by Addition of a DDSBiocomposite Additive to Thermoplastic Resins

In Example 2 the recommended processing temperature of the PCCRC was450° F. The PCCRC was mixed with 5% by weight DDS biocomposite additiveas described in Example 1, and loaded into the feed hopper of theextruder. As the material was being extruded the temperature was rampeddown in 50° F. increments and allowed to stabilize at each step. Theextrusion energy was monitored by the amp draw of the drive motor andthe quality of the extrusion was monitored by inspection.

The temperature was reduced to 400° F., 350° F. and 300° F. For thefirst two increments there was no measured increase in amp draw. Theextrusion rate and quality of the extrusion product did not change. At300° F. the amp draw increased approximately 15%. The extrusion productbegan to show inclusions of material that had not melted and combinedhomogeneously with the other materials.

The addition of 5% DDS biocomposite additive, as described in Example 1,to the PCCRC material allowed the processing temperature to be reducedat least 100° F. below the recommended processing temperature with nomeasurable effect on the extruder energy requirement or visible effecton the quality of the extrusion product.

Example 4 Reduction of Material Required for a Part by Addition of a DDSBiocomposite Additive to Produce Foam

11 melt high density polyethylene (HDPE) was used to create 47 inch testdisks by injection molding using a 375 ton, multi-nozzle, low pressurestructural foam molding machine that was fully hydraulic with a 4.5 inchextruder.

The first test disks were made using only native HDPE with no foamingagent or other additives. The native HDPE disk weight was 30.4 lbs. Thesecond test disks were made using a mixture of HDPE and 5% DDSbiocomposite additive, as described in Example 1. The weight of thesecond test disk was 22.0 lbs.

The use of 5% DDS biocomposite additive, as described in Example 1, withHDPE in injection molding reduced the material requirement for the partby approximately 28%. The excess material was displaced by gas bubblesproduced by the DDS biocomposite additive, as described in Example 1,during processing.

The foregoing discussion discloses and describes merely exemplaryembodiments. Upon review of the specification, one of ordinary skill inthe art will readily recognize from such discussion, and from theaccompanying figures and claims, that various changes, modifications andvariations can be made therein without departing from the spirit andscope of the invention as defined in the following claims.

What is claimed is:
 1. A process comprising: mixing about 80 to 95weight percent of a thermoplastic with a dried distillers solublesbiocomposite comprising 30 to 90 weight percent dried distillerssolubles, 5 to 20 weight percent metal oxide; and 5 to 50 weight percentfiber to form a mixture, wherein the weight percents are based on atotal weight of the biocomposite, wherein the biocomposite has amoisture content of 0.5 to 15 percent; and melt processing the mixtureat a temperature below a melt processing temperature of thethermoplastic by itself.
 2. The process of claim 1, wherein thetemperature is about 10 to about 35 percent less than the meltprocessing temperature of the thermoplastic.
 3. The process of claim 1,further comprising adding a latex compound to the mixture.
 4. Theprocess of claim 1, further comprising adding ethylene oxide to themixture.
 5. The process of claim 1, wherein the thermoplastic comprisestwo or more different thermoplastics, wherein at least one of the twothermoplastics is incompatible with at least one of the otherthermoplastics when melt processed without the dried distillersbiocomposite, and wherein melt processing produces a homogenousmaterial.
 6. The process of claim 5, wherein the two or more differentthermoplastics comprise at least one recycled plastic.
 7. The process ofclaim 1, wherein the thermoplastic is selected from the group consistingof polyamides, polyolefins, polyvinyl chloride, polyacrylate,polyacetate, polystyrene, styrene-acrylonitrile copolymer, and mixturesthereof.
 8. The process of claim 1, wherein the dried distillerssolubles biocomposite is in a powder form.
 9. The process of claim 1,wherein the dried distillers solubles biocomposite is in a granularform.
 10. The process of claim 1, wherein the dried distillers solublesbiocomposite is in a pellet form.